JP3244700B2 - Liquid laundry detergent containing boric acid-diol complex that inhibits citric acid, cellulase, and proteolytic enzymes - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to anionic or nonionic surfactants, citric acid or water-soluble salts thereof, proteolytic enzymes, cellulases, 1,2-propanediol (hereinafter “diol”).
) And boric acid or a derivative thereof (hereinafter referred to as “boric acid”). The composition is made by adding the diol and boric acid to the composition before adding the citric acid / salt to the composition. This order of addition improves the stability of cellulase in the presence of proteolytic enzymes.

BACKGROUND OF THE INVENTION A problem commonly encountered with protease-containing liquid detergents is the degradation of other enzymes in the composition by proteolytic enzymes. The stability of other enzymes on storage and their performance are impaired by proteolytic enzymes.

Boric acid and Boronic acid are known to reversibly inhibit proteolytic enzymes.
For a discussion of the inhibition of subtilisin, a serine protease by boronic acid, see Philipp, M. and Bender, M.
L., 'Kinetics of Subtilisin and Thiolsubtilisin'
(Dynamics of subtilisin and thiols subtilisin), M
olecular & Cellular Biochemistry, vol.51, pp.5-32
(1983).

One type of boronic acid, the peptide boronic acid, was produced in December 1988.
European Patent Application No. 293 of kettner et al.
No. 881, especially in medicine, as an inhibitor of a trypsin-like serine protease.

In liquid detergents built with citric acid or a water-soluble salt thereof, boric acid appears to complex with citric acid / salt. This is thought to adversely affect the function of boric acid as a protease inhibitor. Therefore, the proteolytic enzyme can freely degrade the cellulase in the composition, rendering it ineffective. The degree to which the citric acid / salt complexes with the boric acid derivative will depend on the type of derivative used in the composition.

The efficacy of boric acid as a protease inhibitor is
It can be increased by the addition of 1,2-propanediol. Without being bound by theory, it is believed that a predominantly 1: 1 molar boric acid-diol complex is formed that binds to and inhibits the proteolytic enzyme active site (serine).

However, the addition of boric acid to a liquid detergent containing citric acid / salt and 1,2-propanediol does not require the addition of boric acid and diol to the composition prior to citric acid in the presence of protease. It was found that the cellulase stability was not significantly improved. During this order of addition, the boric acid / diol mixture becomes an effective protease inhibitor even in the presence of citric acid or its salts. This minimizes the degradation of cellulases by proteolytic enzymes. Upon dilution with water, such as under typical wash conditions, proteolytic enzymes are no longer inhibited and can function to remove protease-sensitive soils from the fabric. It is not disclosed in the art that it is important to add boric acid and diol to the liquid detergent composition containing proteolytic enzymes and cellulases before adding the citric acid / salt. It is particularly surprising that citric acid / salt does not neutralize boric acid / diol complexes with respect to protease inhibition over time.

Aronson et al., European Patent Application 381 262, published August 8, 1990, discloses a mixture of proteolytic and lipolytic enzymes in a liquid medium. It is said that the stability of the lipolytic enzyme is improved by the addition of a stabilizer system containing a boron compound and a polyol which can react therewith, whereby the polyol is at least
It has a temporary binding number of 500 / mol and a secondary binding constant with the boron compound of at least 1000 ² / mol ² .

German Patent No. 3,918,761 to Weiss et al., Published June 28, 1990, discloses a liquid enzyme concentrate which can be used as a starting solution for producing liquid detergents and the like. The concentrate contains hydrolase, propylene glycol and boric acid or a soluble salt thereof.

U.S. Pat. No. 4,900,475 to Ramachandran et al., Issued Feb. 13, 1990, discloses a stabilizing agent containing a surfactant, a builder salt and an effective amount of an enzyme or enzyme containing protease or alpha-amylase enzyme. An enzyme-containing detergent is disclosed. The composition also contains a stabilizing system composed of glycerin, a boron compound and a carboxylic acid compound of 2 to 8 carbon atoms.

Severson, Jr., U.S. Pat. No. 4,537,707, issued Aug. 27, 1985, discloses a heavy duty containing anionic surfactants, fatty acids, builders, proteolytic enzymes, boric acid, calcium ions and formate. Describes liquid detergents. The combination of boric acid and formate shows improved proteolytic enzyme stability in the composition.

European Patent Application No. 80 223 to Boskamp et al., Published June 1, 1983, contained boric acid or an alkali metal borate together with a reduced alkali metal salt together with a polyfunctional amino compound or polyol. An aqueous enzyme detergent composition is described.

Similarly, Boskamp's GB published on January 20, 1982
In US Pat. No. 2,079,305, high enzyme stability is defined as
It is disclosed that a 1: 1 or more mixture of boric acid and polyol and a cross-linked neutralized polyacrylate polymer can be obtained in a built liquid detergent composition.

SUMMARY OF THE INVENTION The present invention provides, by weight: a. About 5-50% of an anionic or nonionic surfactant
(Where at least about 25% is an ethoxylated or sugar-based surfactant); b. About 1-10% of citric acid or a water-soluble salt thereof; c. About 1-20 of 1,2-propanediol. D. About 0.5-5% of boric acid or a derivative thereof; e. 0.0001-1.0% of active protease; f. About 0.0001-1.0% of active cellulase enzyme; and g. About 10-75% of water. The invention relates to a liquid laundry detergent composition comprising: adding 1,2-propanediol and boric acid or a derivative thereof to a composition before adding citric acid or a salt thereof to the composition.

DESCRIPTION OF THE INVENTION The present liquid laundry detergent composition comprises an anionic or nonionic surfactant or a mixture thereof, citric acid or a water-soluble salt thereof, 1,2-propanediol, boric acid or a derivative thereof, a proteolytic enzyme, a cellulase. And water. The composition is made by adding 1,2-propanediol and boric acid or a derivative thereof to the composition before adding the citric acid or salt to the composition. This order of addition significantly increases the stability of cellulase in the presence of proteolytic enzymes.

Surfactants The compositions of the present invention comprise about 5 to 50, preferably about 10 to 40, most preferably about 12 to 30% by weight of an anionic or nonionic surfactant. Mixtures of these surfactants are also contemplated in the present invention. It is preferable that a significant amount of a surfactant is not contained other than the anionic and nonionic surfactants.

A preferred cellulase in the present invention is modified with an alkyl sulfate and a linear alkyl benzene sulfonate anionic surfactant. Ethoxylation and sugar substrate detergents prevent such denaturation of cellulases. Therefore, at least 25% by weight of surfactant,
Preferably at least 50%, more preferably at least 75%
Is preferably an ethoxylated and / or sugar substrate anionic or nonionic surfactant.

Preferred anionic surfactants herein, C ₁₂ -C ₁₈ alkyl sulfates and C for good cleaning performance
₁₁ -C ₁₃ linear alkylbenzene sulfonates, the alkyl sulfates 1 to the modification of the cellulase by for the alkyl sulfates and alkylbenzene sulfonates surfactants good cleaning minimizes
C ₁₂ -C ₁₈ alkyl sulfates ethoxylated with moles per average about 1-6 moles of ethylene oxide and the like. Preferably, nonionic surfactants are C ₁₀ -C ₁₈ alcohol with an alcohol per mole 2-20 (preferably about 5-12) mole of the condensation product or polyhydroxy C _12-18 (preferably with ethylene oxide C _11-15 ) Fatty acid amide. These and other surfactants useful herein are described in further detail below.

Anionic surfactants Alkyl ester sulfonate surfactants can be utilized in the present invention. These are desirable because they are derived from renewable non-oil resources. The preparation of the alkyl ester sulfonate surfactant component is according to known methods disclosed in the technical literature. For example, linear esters of C ₈ -C ₂₀ carboxylic acids, 'The Journal of the America
n Can be sulfonated with gaseous SO ₃ according to Oil Chemists Society ', 52 (1975), pp. 323-329. Suitable starting materials include natural fatty substances such as those derived from tallow, coconut and coconut oil and the like.

Preferred alkyl ester sulfonate surfactants have the following structural formula: Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl or a combination thereof, and M is a soluble salt-forming cation. Suitable salts include metal salts such as sodium, potassium and lithium salts, methyl, dimethyl, trimethyl and quaternary ammonium cations, substituted or unsubstituted ammonium salts such as tetramethylammonium, dimethylpiperidinium and alkanolamines, For example, cations derived from monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates wherein R ³ is C ₁₄ -C ₁₆ alkyl is especially preferred.

Alkyl sulfate surfactants are another type of useful anionic surfactant.

Includes water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably C ₁₀ -C ₂₀
M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium), methyl, dimethyl, trimethylammonium and alkyl or hydroxyalkyl having an alkyl component, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl. Quaternary ammonium cations, for example, substituted or unsubstituted ammonium cations such as tetramethylammonium, cations derived from alkanolamines such as dimethylpiperidinium and ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like. In particular, C _12-16 alkyl chains are preferred at low wash temperatures (eg, below about 50 ° C.) and C _16-18
Alkyl chains are preferred at high wash temperatures (eg, above about 50 ° C.).

Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactants. These surfactants typically have the formula RO (A) _m SO ₃ M
Wherein R is unsubstituted C ₁₀ -C ₂₄
Hydroxyalkyl groups having an alkyl or C ₁₀ -C ₂₄ alkyl component, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy (preferred) or propoxy A unit, m is greater than 0, typically about 0.5 to about 20, more preferably about 1 to about 4, and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium, calcium, Magnesium, etc.), ammonium or substituted ammonium cations. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium, alkanolamines such as cations derived from monoethanolamine, diethanolamine and triethanolamine. There is a mixture of them. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -
C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) a sulfate, wherein M is preferably sodium and potassium Is selected from

Alkyl ethoxy carboxylates surfactant of the present invention have the _{formula: RO (CH 2 CH 2 O} ) x CH 2 COO - M + wherein, R is C ₈ -C ₁₈ (preferably C ₁₂ -C ₁₈₎ X is an average number of about 1 to 15 (preferably about 2 to 6), and M is an alkali metal or alkaline earth metal cation (preferably sodium or potassium). Alkyl chains having about 8 to about 18 carbon atoms can be derived from fatty alcohols, olefins, and the like. Usually and preferably, the alkyl chain is a mixture of alkyl chains. However, pure alkyl chains can also be used. Preferably, the alkyl chain is a straight-chain saturated alkyl chain, but it may be a branched and / or unsaturated alkyl chain. These surfactants and their method of manufacture are:
19, which is hereby incorporated by reference.
European Patent Application No. 90305468.2 published November 28, 90
It is described in the specification.

The addition of anionic surfactant which can be contained in the composition include salts (e.g., sodium, potassium, ammonium and mono-, the substituted ammonium salts such as di- and triethanolamine salts), C ₉ - C ₂₀ linear alkyl benzene sulfonates, C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C ₂₄ olefin sulfonates, for example the United Kingdom, as described in patent specification No. 1,082,179, the heat of citric acid alkaline earth metal Of sulfonated polycarboxylic acid, alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, acyl isothionate produced by sulfonation of the decomposition product UNA isothionate,
N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinate cinnamate and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially, saturated and unsaturated C ₆ -C ₁₄ diesters), N- acyl sarcosinates, alkyl alkyl polysaccharide sulfate (nonionic nonsulfated compounds such as sulfates of alkylpolyglucoside are described below), branched primary alkyl sulfates And fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids, such as rosin, which is present in or derived from tall oil,
Also suitable are hydrogenated rosins and resin acids and hydrogenated resin acids. Further examples are 'Surface Active Agents and Detergent'
s' (Vol.I and II by Schwartz, Perry and Berch). A variety of such surfactants are typically 19
U.S. Patent No. 3, issued to Laughlin et al. On December 30, 1975.
No. 929,678, column 23, line 58 to column 29, line 23 are also disclosed (the disclosure is incorporated herein by reference).

Nonionic Detergents Suitable nonionic detergent surfactants are described in U.S. Pat.No. 3,929,678 to Laughlin et al., Issued Dec. 30, 1975, which is hereby incorporated by reference. At column 13, line 14 to column 16, line 6. Exemplary, non-limiting species of useful nonionic surfactants are listed below.

1. Condensates of alkylphenols with polyethylene, polypropylene and polybutylene oxide. Generally, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols with alkyl phenols having alkyl groups containing from about 6 to about 12 carbon atoms in either a straight or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount corresponding to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630 sold by GAF;
Triton ^™ X-4 sold by Rohm & Haas Company
5, X-114, X-100 and X-102. These compounds are alkylphenol alkoxylates (eg,
(Alkylphenol ethoxylate).

2. Condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol is straight-chain or branched, primary or secondary, and usually about 8 to about
Contains 22 carbon atoms. Particularly preferred is the condensation product of an alcohol having an alkyl group containing from about 10 to about 20 carbon atoms with about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of this type of commercially available nonionic surfactants, generates condensation of ^{Tergitol TM 15-S-9 (} C 11 -C 15 linear secondary alcohol with 9 moles ethylene oxide sold by both Union Carbide Corporation Inc. object),
Tergitol ^™ 24-L-6 NMW (narrow molecular weight distribution condensation product of C ₁₂ -C ₁₄ primary alcohol and 6 moles of ethylene oxide); Neodol sold by Shell Chemical Company
^TM 45-9 (C ₁₄ -C ₁₅ condensation product of linear alcohol with 9 moles ethylene _{^{oxide), Neodol TM 23-6.5 (C 12}} -C
₁₃ Condensation product of linear alcohol with 6.5 mol of ethylene oxide), Neodol ^™ 45-7 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 7 mol of ethylene oxide), Neodol ^™
45-4 (C ₁₄ -C ₁₅ condensation product of linear alcohols with ethylene oxide 4 mol); The Procter & Gamble Compa
Kyro ^TM EOB sold by ny, Inc. (C ₁₃ -C ₁₅ condensation product of linear alcohol with 9 moles ethylene oxide) is.
This category of nonionic surfactants is commonly called "alkyl ethoxylates".

3. Condensation products of ethylene oxide and a hydrophobic base formed by condensation of propylene oxide and propylene glycol. The hydrophobic portion of these compounds is preferably about 15
It has a molecular weight of 00 to about 1800 and is water-insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and the liquid properties of the product have a polyoxyethylene content that corresponds to condensation with ethylene oxide within about 40 moles. Is retained until about 50% of the total weight of the condensation product. Examples of this type of compound include certain commercially available Pluronic ^™ surfactants sold by BASF.

4. Condensation products of ethylene oxide and products obtained from the reaction of propylene oxide and ethylenediamine.
The hydrophobic portion of these compounds consists of the reaction product of ethylenediamine and excess propylene oxide, usually about 25%.
It has a molecular weight of 00 to about 3000. The hydrophobic moiety is condensed with ethylene oxide to an extent that the condensation product contains about 40 to about 80% by weight polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. Examples of nonionic surfactants of this type include one commercially available Tetr from BASF
There are onic ^™ compounds.

5. A semi-polar, water-soluble amine oxide having one alkyl moiety of from about 10 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl group containing from about 1 to about 3 carbon atoms and a hydroxyalkyl group. Nonionic surfactant. Preferred amine oxide surfactants (most preferably _{C 12 -C 16) C 10 -C} 18 alkyl dimethyl amine oxide.

6.about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms
A hydrophobic group comprising a polysaccharide such as a polyglycoside and about 1 to about
A sugar substrate nonion such as an alkyl polysaccharide disclosed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 21, 1986, having a hydrophilic group containing 10, preferably from about 1.3 to about 3, sugar units. Surfactant. 5 or 6 carbon atoms
Any reducing sugar can be used, including, for example, glucose,
Galactose and galactosyl moieties can also be used in place of the glucosyl moiety (optionally, a few hydrophobic groups,
Linked at position 4, etc., thus giving glucose or galactose instead of glucoside or galactoside).
The intersugar linkage is, for example, between one site of the additional saccharide unit and positions 2, 3, 4, and / or 6 of the previous saccharide unit.

In some cases, although not desirable, there may be a polyalkylene oxide chain connecting the hydrophobic moiety and the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, containing about 8 to about 18, preferably about 10 to about 16 carbon atoms.
There are branched or unbranched alkyl groups. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and / or the polyalkylene oxide chain can be up to about 10, preferably 5
The following alkylene oxide moieties can be included. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl,
Di, tri, tetra, penta and hexaglucoside, galactoside, lactoside, glucose, fructoside,
Fructose and / or galactose. Suitable mixtures include coconut alkyl, di, tri, tetra and pentaglucoside and tallow alkyl tetra, penta and hexaglucoside.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof. Wherein the alkyl group contains about 10 to about 18, preferably about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2, and t is 0 to about 10,
Preferably is 0; x is about 1 to about 10, preferably about 1.3
~ 3. Preferably, glycosyl is derived from glucose. To produce these compounds,
The alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form a glucoside (bonded at position 1). The additional glycosyl units may then be in their 1-position and the previous glycosyl units 2, 3, 4, and / or 6-position,
Preferably, it can be mainly bonded to the 2-position.

7. Fatty acid amide surfactant having the formula: In the above, R ⁶ is about 7 to about 21 (preferably about 9 to about 17)
Wherein each R ⁷ is hydrogen, C _1-
C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and - (C ₂ H ₄
O) _x H, wherein x is from about 1 to about 3. Preferred amides are C ₈ -C ₂₀ ammonia amides, monoethanolamides, diethanolamides, and isopropanol amides.

8. Polyhydroxy fatty acid amide surfactant of the following structural formula: R ¹ in the above H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁
Or C ₂ alkyl, most preferably C ₁ alkyl (ie,
Methyl); R ² is C ₅ -C ₃₁ hydrocarbyl, preferably straight-chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight-chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight-chain C _11-. Z is C ₁₅ alkyl or alkenyl, or a mixture thereof; Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or Propoxylation). Z
Is preferably derived from a reducing sugar in a reductive amination reaction;
More preferably, Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As a raw material, not only the individual sugars described above,
High dextrose corn syrup, high fructose corn syrup and high maltose corn syrup are also available. It should be understood that these corn syrups may form a mix of sugar components with respect to Z and are not intended to exclude other suitable ingredients. Z is preferably _{-CH 2 - (CHOH) n -CH} 2 OH, -CH (CH 2 OH)
-(CHOH) _n-1 -CH ₂ OH, -CH _2- (CHOH) ₂ (CHOR ')
(CHOH) is selected from -CH ₂ OH and the group consisting of alkoxylated derivatives, where n is an integer from 3 to 5, R 'is H or a cyclic or aliphatic monosaccharide. n
Glycityls There is 4, particularly _{-CH 2 - (CHOH) 4 -CH} 2 OH
Is most preferred.

In the above formula, R ′ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N
-2-hydroxyethyl or N-2-hydroxypropyl.

R ² —CO—N <is, for example, cocamide, stearide, oleamide, lauramide, myristamide, capricamide,
Palmitamide, tallowamide and the like.

Z is 1-deoxyglucityl, 2-deoxyfrucchityl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotriotyl and the like. is there.

Methods for making polyhydroxy fatty acid amides are known in the art. Generally, they react an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine, followed by a condensation / amidation step to convert the N-alkyl polyhydroxyamine to a fatty acid fatty ester or triglyceride. To form an N-alkyl, N-polyhydroxy fatty acid amide product. Methods for producing polyhydroxyfatty acid amide-containing compositions are described, for example, in GB Patent Specification No. 809,060 published February 18, 1959, U.S. Pat.No. 2,965,576, ERWilson issued December 20, 1960.
Anthony M. Schwartz, U.S. Pat.No. 2,703,798, issued Mar. 8, 955, and Piggott, U.S. Pat.No. 1,985,424, issued Dec. 25, 1934, each of which is disclosed in US Pat. Citation is made a part of the disclosure of this specification.

Citric acid The composition further contains about 1 to 10, preferably about 1.5 to 8% by weight of citric acid. Water soluble salts of citric acid, especially the sodium salts, are also useful in the present liquid detergent compositions.

Diol / Boric Acid Mixture The present liquid detergent composition contains a mixture of 1,2-propanediol and boric acid or a derivative thereof. The final concentration of boric acid or its derivative in the detergent composition is about 0.5-5
%, And the final concentration of 1,2-propanediol is about 1-20% by weight. Preferably, the concentration of boric acid or a derivative thereof in the composition is about 1-4% by weight, most preferably about 1.5-3% by weight. The concentration of the diol in the composition is preferably about 3-15, most preferably about 5-12% by weight.

The diol / boric acid weight ratio is preferably about 1: 1 to 20: 1,
More preferably, it is about 2: 1 to 10: 1. This is preferred 1: 1
Additional diols are added to ensure sufficient diol to form the molar diol / borate complex, and to aid dissolution of other components during processing and storage.

Suitable boric acid derivatives include borax, boron oxide, polyborate, orthoborate, pyroborate, metaborate or mixtures thereof. Preferred compounds are the alkali salts of boric acid, such as sodium borate, and their amine salts, such as the monoethanolic salt of boric acid. These salts can be formed in the formulation by in situ neutralization of boric acid with a suitable alkali or amine.

Proteolytic enzyme The liquid detergent composition is present in an amount of about 0.0001-1.0, preferably about 0.001.
005-0.3, most preferably about 0.002-0.1% by weight of active proteolytic enzyme. The protease may be a mixture. Proteolytic enzymes may be of animal, plant or microbial (preferred) origin. Serine proteases of bacterial origin are more preferred. Purified or unpurified forms of this enzyme can also be used.
Proteolytic enzymes produced by chemically or genetically altered variants are also included. Bacterial serine proteases obtained from Bacillus subtilis and / or Bacillus licheniformis are particularly preferred.

 Suitable proteolytic enzymes include commercially available Alca
lase , Esperase , Savinase , Maxatase , Maxaca
l , Maxapem 15 And subtilisin BPN and BPN '
You. Preferred proteolytic enzymes include, in particular,
Filed on April 28, 1987, called "Protease B"
European Patent Application No. 87303761.8 (particularly,
Pages 24 and 98) and here,
A modified bacterial serine protein component called "ase A"
Venegas published on October 29, 1986 on degrading enzymes
Of European Patent Application No. 199,404
Modified bacterial serine proteases, such as
You.

Cellulase The third essential component in the present liquid composition is a cellulase enzyme. It is a bacterial or fungal cellulase.

The amount of cellulase used in the composition will vary depending on the type of cellulase and the intended use. Generally from about 0.0001 to 1.0, more preferably on a cellulase activity basis.
0.0002-0.5% by weight is used. Preferably, the cellulase has an optimum pH between 5 and 9.5. The amount of cellulase is preferably 0.005 to 40 mg / liter of washing solution, more preferably the amount of enzyme protein released in the washing solution.
The amount is 0.01 to 10 mg / liter of the washing solution.

Suitable cellulases are described in Barbesga, published March 6, 1984, which is hereby incorporated by reference.
U.S. Pat. No. 4,435,307 to Ard et al., in which Humicola i.
nsolens) are disclosed. Suitable cellulases are described in GB-A-2.075.028, G, all of which are incorporated herein by reference.
It is also disclosed in BA-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are those produced by Humicola insolens strains (Humicola grisea var. Thermoidea), especially cellulases produced by Humicola strain DSM 1800, fungi of Bacillus N or cellulase 212 producing fungi belonging to the genus Aeromonas. Cellulase and marine mollusks (Dolabella Auricula Solander)
Is a cellulase extracted from hepatopancreas.

Here, the activity measurement for cellulase is based on the hydrolysis of carboxymethylcellulose. The produced reduced carbohydrates were obtained from WSHoffman, 'J. Biol. Chem.', 120, 51.
Colorimetrically by ferrocyanide reaction as described in (1973). An important condition for incubation is pH =
7.0, temperature of 40 ° C and incubation time of 20 minutes.

One CMCase unit is defined as the amount of enzyme that forms an amount of reduced carbohydrate per minute equivalent to 10 ^-6 moles of glucose under the above conditions.

The useful range of cellulase activity in this relationship is 0.01 to
1360, preferably 0.1-140, CMCase activity units / gram of detergent composition.

Preferred cellulases herein consist essentially of a homologous endoglucanase component that is immunoreactive with an antibody to highly purified about 43 kD endoglucanase from Humicola insolens, DSM 1800, or is homologous to the about 43 kD endoglucanase. Things. The endoglucanase component is preferably at least 50 CMC endoase units / mg of protein, more preferably at least 60 CMC endoase units / mg of total protein, especially at least 90 CMC endoase units / mg of total protein, most preferably at least 100 CMC endoase units / total. It has endoglucanase activity of mg protein. Preferably, the endoglucanase component has an isoelectric point of about 5.1.

Such cellulases and methods of making them are described in Novo Nor, incorporated herein by reference.
This is described in PCT International Publication No. WO 91/17243 published on November 14, 1991 by disk A / S.

Water The composition comprises from about 10 to about 75, preferably from about 25 to about 60% by weight.
Contains water.

Optional Ingredients Other Detergent Builders In addition to the citric acid / salt described above, the composition contains 0 to about 50, more preferably about 2 to 30, most preferably about 3 to 15% by weight of another detergent builder. Inorganic and organic builders can be used.

Inorganic detergent builders include polyphosphates (exemplified by tripolyphosphate, pyrophosphate and glassy polymerized metaphosphate), phosphonates, phytic acids, silicates, carbonates (including bicarbonates and sesquicarbonates), alkali metals of sulfates and aluminosilicates , Ammonium and alkanol ammonium salts, but are not limited to.

Preferred organic detergent builders for the purposes of the present invention include various polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having multiple carboxylate groups, preferably at least two carboxylate.

The polycarboxylate builder can usually be added to the composition in the acid form, but may also be added in the form of a neutralized salt. When utilized in acid form, alkali metal or alkanol ammonium salts such as sodium, potassium and lithium are preferred.

Among the polycarboxylate builders are various categories of useful substances. One important category of polycarboxylate builders includes ether polycarboxylates. Several ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates include Berg U.S. Patent Nos. 3,128,287 and 1,1972, issued April 7, 1964, both of which are incorporated herein by reference. There are oxydisuccinates as disclosed in US Pat. No. 3,635,830 to Lamberti et al.

Still other ether polycarboxylates include copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6
-Trisulfonic acid and carboxymethyloxysuccinic acid.

Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acid. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Also included are polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and their soluble salts.

Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Pat. No. 3,723,322 to Diehl, issued Mar. 28, 1973, which is hereby incorporated by reference. There is.

In the detergent compositions of the present invention, the 3,3 disclosed in Bush U.S. Pat.No. 4,566,984, issued Jan. 28, 1986, which is hereby incorporated by reference.
-Dicarboxy-4-oxa-1,6-hexanedioate and related compounds are also suitable. Useful succinic acid builders is C ₅ -C ₂₀ alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Alkyl succinic acids typically have the general formula R-
CH (COOH) CH ₂ (COOH), a derivative of succinic acid, wherein R is a hydrocarbon, such as C ₁₀ -C ₂₀ alkyl or alkenyl, preferably C ₁₂ -C ₁₆ , or R is hydroxyl , Sulfo, sulfoxy or sulfone substituents, all as described in said patent.

The succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of the succinate builder include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinate is the preferred builder in this group, 1986
European Patent Application No. 86200690.5 / 0,2 published on November 5,
No. 00,263.

Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (about 2000 or more). (These polyacrylates having a molecular weight of 0.1% can also be effectively used as dispersants) and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetals disclosed in US Patent No. 4,144,226 to Crutchfield et al., Issued March 13, 1979, which is hereby incorporated by reference. Carboxylate. These polyacetal carboxylates can be prepared by combining an ester of glyoxylic acid and a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then attached to a chemically stable end group to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and converted to a surfactant. Added to the agent.

Polycarboxylate builders are also disclosed in Diehl U.S. Pat. No. 3,308,067, issued March 7, 1967, which is hereby incorporated by reference. Such substances include maleic acid,
There are water soluble salts of homo and copolymers of aliphatic carboxylic acids such as itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.

Preferred polycarboxylate builders for use herein having the general formula: CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B) wherein A is hydroxyl; B is hydrogen or-
O-CH (COOX) be -CH ₂ (COOX); X is hydrogen or a salt forming cation. When B is H, the compound is monosuccinic acid tartrate (TMS) and its water-soluble salts. In the above α-hydroxy acid (TMS), A is H and B is —O
It is preferably mixed with tartaric acid disuccinic acid (TDS) represented by the above chemical structure being —CH (COOX) —CH ₂ (COOX). Particularly preferred is a mixture of TMS and TDS in a weight ratio of about 97: 3 to about 20:80, most preferably 80 TMS: 20 TDS. These builders are disclosed in U.S. Pat. No. 4,663,071, issued May 5, 1987 to Bush et al.

Other organic builders known in the art can also be used. For example, a monocarboxylic acid having a long-chain hydrocarbyl and a soluble salt thereof can be used. These are usually "soaps"
Contains substances called. A chain length of C ₁₀ -C ₂₀ is typically utilized. The hydrocarbyl may be saturated or unsaturated.

Other optional ingredients Other active ingredients, other enzymes, waste release agents, waste suspensions,
Various other ingredients useful in detergent compositions, including brighteners, suds suppressors, carriers, hydrotropes, processing aids, dyes or contents, solvents, bleach, bleach activators, and the like, are included in the composition. Can be contained.

The liquid detergent composition can contain other solvents such as low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred for dissolving the surfactant, but polyols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups (eg, ethylene glycol and glycerin) can also be used.

Preferably, the present liquid laundry detergent compositions are formulated such that they have a pH of about 6.5 to 11.0, preferably about 7.0 to 9.5, in a 10% solution in water at 20 ° C. Techniques for controlling the pH at the recommended amount include the use of buffers, alkalis, acids and the like, which are well known to those skilled in the art.

A concentrated liquid detergent composition is preferred here. By "concentrate" is meant a composition that delivers the same amount of active ingredient to the laundry in a lesser amount. The typical standard usage of a strong liquid is 118 ml (about 1/2 cup) in the United States and 180 ml in Europe.

Concentrated strong liquid is about 10-100% by weight than standard strong liquid
It contains many active ingredients and is dosed in 1/2 cup or less depending on their activity level. The present invention is more useful with concentrated formulations because there are many active agents that interfere with enzyme performance. About 30-90, preferably
Heavy liquid laundry detergent compositions containing 40-80, most preferably 50-70% by weight of the active ingredient are preferred.

The following examples illustrate the compositions of the present invention. All parts, percentages and ratios used herein are by weight unless otherwise indicated.

Examples 1 to 6 The following liquid laundry detergent compositions are prepared by mixing the components in the order given. Examples 2 to 6 are compositions according to the invention. Comparative Example 1 is Example 1 after boric acid is citric acid.
Example 2 differs from Example 2 in that it is added to the composition of In the table, the following abbreviations are used.

C ₄₅ E _2.25 S is C _14-15 alkyl polyethoxylate (2.
25) It is a sulfonic acid.

C ₂₃ E _6.5 T is a C _12-13 alkyl ethoxylate (6.5) that has been distilled to remove non-ethoxylated and monoethoxylated alcohols.

 MEA is monoethanolamine.

C ₂₄ glucamides is C _12-14 alkyl N- methyl glucamide. TEPA-E _15-18 at each hydrogen site on each nitrogen 15-18
Tetraethylenepentymine ethoxylated with molar (average) ethylene oxide.

Fatty acids are _C12-14 fatty acids.

NaTS is sodium mono- and di-succinate tartrate (80:20
Mix).

 Na formate is sodium formate.

 Ca formate is calcium formate.

The protease was protease B as described above (34 g /
).

Cellulase consists essentially of the 43 kD endoglucanase (12 g /) described in PCT International Publication No. WO 91/17243.

SRP is the soil release polymer of US Pat. No. 4,968,451.

The compositions of Examples 1, 2, 3 and 5 are evaluated for cellulase stability after storage at the specified temperature and time and are determined as a percentage of the initial performance exhibited by the cellulase in the composition. In this evaluation, used cotton fabric was washed with the test composition, tumble dried in an automatic dryer (preferred over line drying), and expertly tested after several washing / drying cycles to restore the fabric appearance. Compare visually. The results are as follows.

From the above it can be seen that the addition of boric acid and 1,2-propanediol to Examples 2 and 5 prior to the addition of citric acid was comparable to Comparative Example
It can be seen that the stability of cellulase is significantly improved as compared with the case of. Improved cellulase stability is also obtained in Example 3.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-57697 (JP, A) Table 7-501349 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/386 C11D 3/04 C11D 3/20

Claims (18)

(57) [Claims] 1. A liquid laundry detergent composition, by weight: a. 5 to 50% of an anionic or nonionic surfactant, wherein at least 25% is an ethoxylated or sugar-based surfactant. B. 1 to 10% of citric acid or a water-soluble salt thereof; c. 1 to 20% of 1,2-propanediol; d. 0.5 to 5% of boric acid or a derivative thereof; e. 1.0%; f. Active cellulase enzyme 0.0001-1.0%; and g. Water 10-75%; prior to adding citric acid or a salt thereof to the composition, 1,2-propanediol and boric acid or A composition produced by adding the derivative to the composition. 2. An anionic or nonionic surfactant.
The liquid detergent composition of claim 1, comprising 10-40%, wherein at least 50% is an ethoxylated or sugar-based surfactant. 3. An anionic surfactant is ethoxylated with an average of 1 to 6 moles of ethylene oxide per mole of C ₁₂ -C ₁₈ alkyl sulfate, alkyl sulfate.
C ₁₂ -C ₁₈ alkyl sulfate or C ₁₁ -C ₁₃ linear alkylbenzene sulfonate, or mixtures thereof, and nonionic surfactants, C ₁₀ -C ₁₈ alcohol with an alcohol per mole 2-20 moles, Condensation product with ethylene oxide, or polyhydroxy C ₁₂ -C ₁₈
It is a fatty acid amide. A liquid detergent composition according to claim 2. 4. An anionic or nonionic surfactant.
The liquid detergent composition according to claim 3, comprising 12-30%, wherein at least 75% is an ethoxylated or sugar-based surfactant. 5. Citric acid or its water-soluble salt is 1.5 to 8%
The liquid detergent composition according to claim 4, comprising a liquid detergent composition. 6. The liquid detergent composition according to claim 5, comprising 3 to 15% of 1,2-propanediol and 1 to 4% of boric acid or a derivative thereof. 7. The liquid detergent composition according to claim 6, comprising 5 to 12% of 1,2-propanediol and 1.5 to 3% of boric acid or a derivative thereof. 8. The liquid detergent composition according to claim 1, wherein the weight ratio of 1,2-propanediol to boric acid or a derivative thereof is from 2: 1 to 10: 1. 9. An amount of active proteinase of 0.0005 to 0.3%.
The liquid detergent composition according to claim 1, comprising a liquid detergent composition. 10. The method according to claim 10, wherein the active protease is 0.0002 to 0.1.
The liquid detergent composition according to claim 6, wherein 11. The liquid detergent composition according to claim 10, comprising 0.002 to 0.5% of an active cellulase enzyme. 12. The cellulase is immunoreactive with an antibody against highly purified 43 kD endoglucanase derived from Humicola insolens DSM 1800, or the 43 kD
The liquid laundry detergent composition of claim 1, consisting essentially of a homogeneous endoglucanase component that is homologous to endoglucanase. 13. An endoglucanase component comprising at least 50 CM
13. The liquid laundry detergent composition according to claim 12, which has endoglucanase activity of C endoase units / mg protein. 14. The liquid laundry detergent composition according to claim 13, wherein the endoglucanase component has an isoelectric point of 5.1. 15. The cellulase is immunoreactive with an antibody against highly purified 43 kD endoglucanase derived from Humicola insolens DSM 1800, or the 43 kD
12. The liquid laundry detergent composition according to claim 11, consisting essentially of a homogeneous endoglucanase component that is homologous to endoglucanase. 16. An endoglucanase component having at least 50 CM
16. The liquid laundry detergent composition according to claim 15, having endoglucanase activity of C endoase units / mg protein. 17. The liquid laundry detergent composition according to claim 16, wherein the endoglucanase component has an isoelectric point of 5.1. 18. The liquid laundry detergent composition according to claim 17, having a pH of 7.0-9.5 in a 10% solution in water at 20 ° C.